KR102516911B1 - Resin composition, molded article and laminate - Google Patents

Abstract

(Problem) To provide a resin composition having high transparency and high surface hardness, chemical resistance and high glass transition temperature. In addition, molded articles and laminates using the resin composition are provided.
(Solution) 5 to 90% by mass of a methacrylic resin (A) containing 99% by mass or more of a structural unit derived from methyl methacrylate and an aromatic vinyl compound (b1) represented by at least the following general formula (1) A resin composition containing 10 to 95% by mass of a vinyl copolymer (B) comprising a structural unit derived from a structural unit represented by the following general formula (2) and a cyclic acid anhydride (b2) represented by the following general formula (2). (R ¹ and R ² in the formula each independently represent a hydrogen atom or an alkyl group) (R ³ and R ⁴ in the formula each independently represent a hydrogen atom or an alkyl group)

Description

Resin composition, molded article and laminate {RESIN COMPOSITION, MOLDED ARTICLE AND LAMINATE}

The present invention relates to a resin composition comprising a methacrylic resin and a vinyl copolymer. Moreover, it is related with the molded article and laminated body containing the said resin composition.

A methacrylic resin excellent in transparency, scratch resistance, weather resistance, etc. is useful as a material for molded articles used for optical members, lighting members, signboard members, decorative members, and the like. However, since methacrylic resin has a low glass transition temperature of about 110°C, there is a problem that molded articles made of the resin are easily deformed by heat.

As a method of increasing the glass transition temperature of a methacrylic resin, a method of polymer blending a copolymer resin (SMA resin) composed of styrene and maleic anhydride with a methacrylic resin is known. For example, in Non-Patent Document 1, polymer blends of various SMA resins having different copolymerization ratios of methacrylic resin and maleic anhydride are studied, and the SMA resin containing 8 to 33% by mass of maleic anhydride is meta It is reported that it is compatible with krill resin and has a higher glass transition temperature than methacryl resin. Further, Patent Literature 1 reports that a polymer blend of a copolymer composed of styrene, maleic anhydride, and methyl methacrylate and a methacrylic resin has a high glass transition temperature and low water absorption. Further, Patent Document 2 discloses a laminate comprising a layer made of a resin composition containing a methacrylic resin and an SMA resin, and a layer made of polycarbonate.

Japanese Unexamined Patent Publication No. 2015-105371 International Publication No. 2015/050051

C. R. BRANNOC K, J. W. BARLOW, and D. R. PAUL, Journal of Polymer Science: Part B: Polymer Physics, Vol. 29, 413-429 (1991)

However, the resin composition obtained by such a method has a problem that the surface hardness and chemical resistance are lowered due to the influence of the SMA resin. By reducing the composition ratio of the SMA resin, the decrease in surface hardness and chemical resistance can be suppressed, but the glass transition temperature of the resulting resin composition becomes insufficient.

The present invention has been made in view of the above problems. The object of this is a resin composition containing a methacrylic resin and an SMA resin, which has high surface hardness, chemical resistance, and high glass transition temperature without reducing the high transparency characteristic of the methacrylic resin, and containing the same. It is to provide molded articles and laminates made by

As a result of repeated research by the present inventors, in the following aspects, it has been found that the above-mentioned problems can be solved, and the present invention has been completed.

[1] 5 to 90% by mass of a methacrylic resin (A) containing 99 mass% or more of structural units derived from methyl methacrylate, and derived from at least an aromatic vinyl compound (b1) represented by the following general formula (1) A resin composition containing 10 to 95% by mass of a vinyl copolymer (B) comprising a structural unit and a structural unit derived from a cyclic acid anhydride (b2) represented by the following general formula (2).

[Formula 1]

(R ¹ and R ² in the formula each independently represent a hydrogen atom or an alkyl group)

[Formula 2]

(R ³ and R ⁴ in the formula each independently represent a hydrogen atom or an alkyl group)

[2] The resin composition according to [1], wherein the methacrylic resin (A) contains 99.5% by mass or more of structural units derived from methyl methacrylate.

[3] The resin composition according to [1] or [2], wherein the methacrylic resin (A) has a syndiotacticity (rr) of 50% or more in tripartite display.

[4] The resin composition according to any one of [1] to [3], containing 30 to 60% by mass of a methacrylic resin (A) and 40 to 70% by mass of a vinyl copolymer (B).

[5] The vinyl copolymer (B) contains 50 to 84% by mass of structural units derived from an aromatic vinyl compound (b1), and 15 to 49% by mass of structural units derived from a cyclic acid anhydride (b2). The resin composition according to any one of [1] to [4], which contains 1 to 35% by mass of a structural unit derived from methacrylic acid ester (b3).

[6] The resin composition according to [5], wherein the methacrylic acid ester (b3) is methyl methacrylate.

[7] The resin composition according to any one of [1] to [6], wherein the resin composition has a glass transition temperature of 115 to 160°C.

[8] The resin composition according to any one of [1] to [7], containing a UV absorber.

[9] The resin composition according to [8], wherein the ultraviolet absorber has a benzotriazole skeleton.

[10] The resin composition according to [9], wherein the ultraviolet absorber has a triazine skeleton.

[11] The resin composition according to any one of [8] to [10], wherein the ultraviolet absorber contains sulfur in its skeleton.

[12] The resin composition according to any one of [8] to [11], containing two or more types of ultraviolet absorbers.

[13] A molded article provided with the resin composition according to any one of [1] to [12].

[14] A laminate comprising a layer made of the resin composition according to any one of [1] to [12] and a layer made of a thermoplastic resin composition (T) having a glass transition temperature in the range of 130 to 160°C.

[15] The laminate according to [14], wherein the thermoplastic resin composition (T) is a resin composition containing polycarbonate.

[16] The laminate according to [14] or [15], wherein the absolute value of the difference between Tg of the thermoplastic resin composition (T) and the resin composition is 30°C or less.

[17] The laminate according to any one of [14] to [16], further comprising a scratch-resistant layer on at least one surface.

The resin composition according to the present invention is a resin composition containing a methacrylic resin and an SMA resin, which does not reduce the high transparency characteristic of the methacrylic resin, and has a high surface hardness, chemical resistance, and high glass transition temperature, and a resin composition thereof. It exhibits the excellent effect of being able to provide molded articles and laminates formed by containing it.

Hereinafter, an example of an embodiment to which the present invention is applied will be described. In addition, the numerical value specified in this specification represents the value obtained when measured by the method described in the Example mentioned later. For example, the weight average molecular weight Mw is a standard polystyrene conversion value measured by GPC (gel permeation chromatography), and shows a value obtained when measured by the method described in the Examples described later. In addition, the numerical value "A to B" specified in this specification represents a range satisfying the numerical value A and a value larger than the numerical value A and smaller than the numerical value B and the numerical value B.

[Resin composition]

The resin composition of the present invention comprises a methacrylic resin (A), a structural unit derived from an aromatic vinyl compound (b1) represented by the following general formula (1), and a cyclic acid anhydride (b2) represented by the following general formula (2) It is formed by containing a vinyl-based copolymer (B) containing a structural unit derived from (hereinafter referred to as "SMA resin (B)").

[Formula 3]

(R ¹ and R ² in the formula each independently represent a hydrogen atom or an alkyl group)

[Formula 4]

(R ³ and R ⁴ in the formula each independently represent a hydrogen atom or an alkyl group)

The range of content of the methacrylic resin (A) in the resin composition of this invention is 5-90 mass %. The content of the methacrylic resin (A) in the resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and most preferably 30% by mass or more. The content of the methacrylic resin (A) in the resin composition is preferably 85% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less, and most preferably 60% by mass or less. The layer made of the resin composition of the present invention has excellent scratch resistance when the content of the methacrylic resin (A) in the resin composition is 5% by mass or more, and when it is 90% by mass or less, when laminated with other layers, under high temperature and high humidity. It is possible to suppress the occurrence of warping in the

The methacrylic resin (A) contains 99% by mass or more, preferably 99.5% by mass or more, more preferably 100 Contains % by mass. When the methacrylic resin (A) contains 99% by mass or more of the structural unit derived from MMA, the heat resistance and chemical resistance of the resin composition of the present invention can be improved. The content of the MMA-derived structural unit of the methacrylic resin (A) is determined by reprecipitation of the methacrylic resin (A) in methanol, and the purified resin is subjected to thermal decomposition and separation of volatile components using thermal decomposition gas chromatography. Thus, it can be calculated from the ratio of the peak areas of the obtained MMA and the copolymerization component (mainly methyl acrylate).

The methacrylic resin (A) contained in the resin composition of the present invention can contain structural units derived from monomers other than MMA in an amount of 1% by mass or less in all monomer units, but it is preferable not to contain such structural units. do.

As said monomer, structural units derived from methacrylic acid esters other than MMA are mentioned. Such methacrylic acid esters include ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, and pentyl methacrylate. methacrylic acid alkyl esters such as hexyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, and dodecyl methacrylate; Methacrylic acids such as 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, cyclooctyl methacrylate, tricyclo[5.2.1.0 ^2,6 ]dec-8-yl methacrylate, etc. Cycloalkyl ester; methacrylic acid aryl esters such as phenyl methacrylate; methacrylic acid aralkyl esters such as benzyl methacrylate; etc. can be mentioned. From the viewpoint of availability, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate are preferred. The total content of structural units derived from methacrylic acid esters other than MMA in the methacrylic resin (A) is preferably 1% by mass or less, more preferably 0.5% by mass or less, and methacrylic acid other than MMA. Those containing no structural units derived from esters are most preferred.

Moreover, as said monomer, structural units derived from other monomers other than methacrylic acid ester are mentioned. Examples of such other monomers include methyl acrylate (hereinafter referred to as "MA"), ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, and 2-acrylic acid. Ethylhexyl, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, acrylic acid 3-methoxybutyl, trifluoromethyl acrylate, trifluoroethyl acrylate, pentafluoroethyl acrylate, glycidyl acrylate, allyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, 3-acrylate Acrylic acid esters, such as dimethylaminoethyl, are mentioned, From a viewpoint of availability, acrylic acid esters, such as MA, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and tert-butyl acrylate, are preferable. And, MA and ethyl acrylate are more preferred, and MA is most preferred. The content of structural units derived from these other monomers in the methacrylic resin (A) is preferably 1% by mass or less in total, more preferably 0.5% by mass or less, and derived from other monomers other than methacrylic acid esters. It is most preferable that it does not contain structural units such as

The methacrylic resin (A) is obtained by polymerizing MMA alone or other monomers which are optional components. In such polymerization, when using multiple types of monomers, usually, after mixing these multiple types of monomers and preparing a monomer mixture, it uses for polymerization. The polymerization method is not particularly limited, but from the viewpoint of productivity, radical polymerization is preferably carried out by methods such as bulk polymerization, suspension polymerization, solution polymerization, and emulsion polymerization.

The lower limit of the syndiotacticity (rr) of the methacrylic resin (A) in triplicate display is preferably 50% or more, more preferably 51% or more, still more preferably 52% or more. When the lower limit of the content of such a structure is 50% or more, the resin composition of the present invention has excellent heat resistance.

Here, the syndiotacticity (rr) of the triad expression (hereinafter sometimes simply referred to as “syndiotacticity (rr)”) is 2 It is the ratio of two chains (two letters, diad) that together are racemo (represented by rr). In addition, in the chain (diad) of structural units in the polymer molecule, those having the same three-dimensional arrangement are called meso, and those having the opposite arrangement are called racemo, and are denoted by m and r, respectively.

The syndiotacticity (rr) (%) of the methacrylic resin (A) was determined by measuring ^{a 1} H-NMR spectrum in deuterated chloroform at 30°C, and using tetramethylsilane (TMS) at 0 ppm from the spectrum. The area (X) of the 0.6 to 0.95 ppm region and the area (Y) of the 0.6 to 1.35 ppm region are measured and calculated by the formula: (X/Y) × 100.

The weight average molecular weight (hereinafter referred to as "Mw") of the methacrylic resin (A) is preferably from 40,000 to 500,000, more preferably from 60,000 to 300,000, still more preferably from 80,000 to 200,000. When the Mw is 40,000 or more, the resin composition of the present invention has excellent mechanical strength, and when it is 500,000 or less, the compatibility with the SMA resin is improved, and the molded article made of the resin composition of the present invention can be improved in transparency.

The glass transition temperature of the methacrylic resin (A) is preferably 100°C or higher, more preferably 105°C or higher, and still more preferably 110°C or higher. When the glass transition temperature is 100°C or higher, the resin composition of the present invention has excellent heat resistance. In addition, the glass transition temperature in this specification is the temperature at the time of measuring by the heating rate of 10 degrees C/min using a differential scanning calorimeter, and calculating by the midpoint method.

The saturated water absorption of the methacrylic resin (A) in water at 23°C is preferably 2.5% by mass or less, more preferably 2.3% by mass or less, and still more preferably 2.1% by mass or less. When the saturated water absorption is 2.5% by mass or less, the resin composition of the present invention has excellent moisture resistance, and can suppress warpage of the laminate due to moisture absorption. In addition, the saturated water absorption in this specification is the mass of a molded article vacuum-dried for 3 days or more, at the time when the molded article is immersed in distilled water at 23 ° C., the mass is measured over time, and equilibrium is reached. It is a value measured as an increase rate of

The melt flow rate (hereinafter referred to as “MFR”) of the methacrylic resin (A) is preferably in the range of 1 to 10 g/10 min. As for the lower limit of this MFR, it is more preferable that it is 1.2 g/10 min or more, and it is still more preferable that it is 1.5 g/10 min. Moreover, as for the upper limit of this MFR, it is more preferable that it is 7.0 g/10 min or less, and it is still more preferable that it is 4.0 g/10 min or less. When the MFR is in the range of 1 to 10 g/10 min, the stability of hot-melting molding is good. In addition, the MFR of the resin composition of the present invention in the present specification is a value measured using a melt indexer at a temperature of 230°C and under a load of 3.8 kg.

The range of content of SMA resin (B) in the resin composition of this invention is 10-95 mass %. The content of the SMA resin (B) in the resin composition is preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, and most preferably 40% by mass or more. The content of the SMA resin (B) in the resin composition is preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less, and most preferably 70% by mass or less. In the laminate of the present invention, when the content of the SMA resin (B) in the resin composition is 10% by mass or more, when laminated with other layers, occurrence of warpage under high temperature and high humidity can be suppressed, and by being 95% by mass or less Excellent abrasion resistance.

The SMA resin (B) is a vinyl copolymer (B) comprising at least a structural unit (b1) derived from an aromatic vinyl compound and a structural unit (b2) derived from a cyclic acid anhydride.

Examples of the alkyl groups independently represented by R ¹ and R ² in the general formula (1) and R ³ and R ⁴ in the general formula (2) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, sec- butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, nonyl group , preferably an alkyl group having 12 or less carbon atoms such as a decyl group and a dodecyl group, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a t-butyl group, and the like A C4 or less alkyl group is more preferable.

As R ¹ , a hydrogen atom, a methyl group, an ethyl group and a t-butyl group are preferable. As R ² , R ³ , R ⁴ , a hydrogen atom, a methyl group and an ethyl group are preferable.

The content of the structural unit derived from the aromatic vinyl compound (b1) in the SMA resin (B) is preferably 50% by mass or more, more preferably 55% by mass or more, and still more preferably 60% by mass or more. The content of the structural unit derived from the aromatic vinyl compound (b1) in the SMA resin (B) is preferably 84% by mass or less, more preferably 82% by mass or less, and still more preferably 80% by mass or less. When this content is in the range of 50 to 84% by mass, the resin composition of the present invention has excellent moisture resistance and transparency. However, when the SMA resin (B) is composed of only two monomers, the aromatic vinyl compound (b1) and the cyclic acid anhydride (b2), the structural units derived from the aromatic vinyl compound (b1) in the SMA resin (B) It is preferable to make content into the range of 50-85 mass %.

Examples of the aromatic vinyl compound (b1) include styrene; Each alkyl-substituted styrene, such as 2-methyl styrene, 3-methyl styrene, 4-methyl styrene, 4-ethyl styrene, and 4-tert- butyl styrene; α-alkyl substituted styrene such as α-methylstyrene and 4-methyl-α-methylstyrene; can be mentioned, and styrene is preferable from the viewpoint of availability. These aromatic vinyl compounds (b1) may be used individually by 1 type, and may use multiple types together.

The content of the structural unit derived from the cyclic acid anhydride (b2) in the SMA resin (B) is preferably 15% by mass or more, more preferably 18% by mass or more, and still more preferably 20% by mass or more. The content of the structural unit derived from the cyclic acid anhydride (b2) in the SMA resin (B) is preferably 49% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less. When the content is in the range of 15 to 49% by mass, the resin composition of the present invention has excellent heat resistance and transparency. However, when the SMA resin (B) is composed of only two monomers of an aromatic vinyl compound (b1) and a cyclic acid anhydride (b2), the structural unit derived from the cyclic acid anhydride (b2) in the SMA resin (B) It is preferable to make content of 15-50 mass % into the range.

Examples of the cyclic acid anhydride (b2) include maleic anhydride, citraconic anhydride, and dimethyl maleic anhydride, and maleic anhydride is preferable from the viewpoint of availability. A cyclic acid anhydride (b2) may be used individually by 1 type, and may use multiple types together.

The SMA resin (B) preferably contains a structural unit derived from a methacrylic acid ester (b3) in addition to the aromatic vinyl compound (b1) and the cyclic acid anhydride (b2). The content of the structural unit derived from the methacrylic acid ester (b3) in the SMA resin (B) is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and 10% by mass It is most preferable that it is % or more. The content of the structural unit derived from the methacrylic acid ester (b3) in the SMA resin (B) is preferably 35% by mass or less, more preferably 30% by mass or less, and still more preferably 26% by mass or less. When this content is in the range of 1 to 35% by mass, transparency and thermal stability are further improved.

Examples of the methacrylic acid ester (b3) include MMA, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, propyl methacrylate, isopropyl methacrylate, and methacrylate. n-butyl acrylate, isobutyl methacrylate t-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 1-phenylethyl methacrylate; etc. can be mentioned. Among these methacrylic acid esters, methacrylic acid alkyl esters having 1 to 7 carbon atoms in the alkyl group are preferable, and MMA is particularly preferable in view of excellent heat resistance and transparency of the obtained SMA resin. Moreover, methacrylic acid ester may be used individually by 1 type, and may use multiple types together.

The SMA resin (B) may have structural units derived from monomers other than the aromatic vinyl compound (b1), the cyclic acid anhydride (b2), and the methacrylic acid ester (b3). Such other monomers include MA, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, acrylic acid. Dodecyl, stearyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, trifluoroacrylate acrylic acid esters such as methyl, trifluoroethyl acrylate, pentafluoroethyl acrylate, glycidyl acrylate, allyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, and 3-dimethylaminoethyl acrylate; there is. These other monomers may be used individually by 1 type, and may use multiple types together. The content of structural units derived from these other monomers in the SMA resin (B) is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 2% by mass or less.

The SMA resin (B) is obtained by polymerizing at least the monomers of an aromatic vinyl compound (b1) and a cyclic acid anhydride (b2). As a monomer, you may add and polymerize the methacrylic acid ester (b3) and the other monomer which is an arbitrary component. In such polymerization, usually, after mixing the monomers to be used to prepare a monomer mixture, it is used for polymerization. The polymerization method is not particularly limited, but from the viewpoint of productivity, radical polymerization is preferably carried out by a method such as bulk polymerization or solution polymerization.

The Mw of the SMA resin (B) is preferably in the range of 40,000 to 300,000. When the Mw is 40,000 or more, the resin composition of the present invention has excellent mechanical strength, and when it is 300,000 or less, the compatibility with the methacrylic resin becomes good, and the transparency of the molded article made of the resin composition of the present invention can be improved. .

The glass transition temperature of the SMA resin (B) is preferably 115°C or higher, more preferably 120°C or higher, and still more preferably 125°C or higher. When the glass transition temperature is 110°C or higher, the resin composition of the present invention has excellent heat resistance and can suppress warping of the laminate due to heat.

The saturated water absorption of the SMA resin (B) in water at 23°C is preferably 1.0% by mass or less, more preferably 0.8% by mass or less, and still more preferably 0.6% by mass or less. When the saturated water absorption is 1.0% by mass or less, the resin composition of the present invention has excellent moisture resistance and can suppress warpage of the laminate due to moisture absorption.

The MFR of the SMA resin (B) is preferably in the range of 1 to 10 g/10 min. As for the lower limit of this MFR, it is more preferable that it is 1.2 g/10 min or more, and it is still more preferable that it is 1.5 g/10 min. Moreover, as for the upper limit of this MFR, it is more preferable that it is 7.0 g/10 min or less, and it is still more preferable that it is 4.0 g/10 min or less. When the MFR is in the range of 1 to 10 g/10 min, the stability of hot-melting molding is good.

The mass ratio (methacrylic resin (A) / SMA resin (B)) of the methacrylic resin (A) and the SMA resin (B) contained in the resin composition of the present invention is to suppress the occurrence of warping under high temperature, transparency, From the viewpoint of scratch resistance, it is preferably in the range of 5/95 to 90/10. This mass ratio is more preferably 10/90 or higher, still more preferably 15/85 or higher, and particularly preferably 20/80 or higher. Moreover, this mass ratio is more preferably 85/15 or less, still more preferably 80/20 or less, and particularly preferably 75/25 or less.

For mixing of the methacrylic resin (A) and the SMA resin (B), a melt mixing method, a solution mixing method, or the like can be used, for example. In the melt mixing method, for example, using a melt kneader such as a uniaxial or multiaxial kneader, an open roll, a Banbury mixer, or a kneader, melt kneading in an inert gas atmosphere such as nitrogen gas, argon gas, or helium gas as necessary. carry out In the solution mixing method, the methacrylic resin (A) and the SMA resin (B) are dissolved in an organic solvent such as toluene, tetrahydrofuran, methyl ethyl ketone, and mixed.

The resin composition of the present invention may contain polymers other than the methacrylic resin (A) and the SMA resin (B) within a range not impairing the effects of the present invention. Examples of such other polymers include polyolefins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene, and ethylene-based ionomers; styrenic resins such as polystyrene, styrene maleic anhydride copolymer, high impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, and MBS resin; methyl methacrylate-styrene copolymer; polyesters such as polyethylene terephthalate and polybutylene terephthalate; Polyamides, such as nylon 6, nylon 66, and a polyamide elastomer; Polyphenylene sulfide, polyether ether ketone, polyester, polysulfone, polyphenylene oxide, polyimide, polyetherimide, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer , thermoplastic resins such as polyacetal and phenoxy resin; Thermosetting resins, such as a phenol resin, a melamine resin, a silicone resin, and an epoxy resin; polyvinylidene fluoride, polyurethane, modified polyphenylene ether, polyphenylene sulfide, silicone modified resin; acrylic rubber, silicone rubber; Styrenic thermoplastic elastomers, such as SEPS, SEBS, and SIS; Olefin type rubbers, such as IR, EPR, and EPDM, etc. are mentioned. Another polymer may be used individually by 1 type, and may use multiple types together.

The content of the other polymer in the resin composition is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 2% by mass or less.

The resin composition of this invention may contain various additives as needed. Examples of such additives include antioxidants, thermal deterioration inhibitors, ultraviolet absorbers, light stabilizers, lubricants, release agents, polymer processing aids, antistatic agents, flame retardants, dyes/pigments, light diffusing agents, gloss removers, impact resistance modifiers, and phosphors. etc. can be mentioned. The content of these additives can be appropriately set within a range that does not impair the effect of the present invention. For example, the content of the antioxidant is 0.01 to 1 part by mass and the content of the ultraviolet absorber is 100 parts by mass of the resin composition. It is preferable that the content of 0.01 to 3 parts by mass and the light stabilizer be 0.01 to 3 parts by mass, the content of the lubricant is 0.01 to 3 parts by mass, and the content of the dye/pigment is 0.01 to 3 parts by mass.

Antioxidant has an effect to prevent oxidative deterioration of resin by itself in the presence of oxygen. For example, a phosphorus antioxidant, a phenolic antioxidant, a sulfur antioxidant, an amine antioxidant, etc. are mentioned. Among these, from the viewpoint of the effect of preventing deterioration of optical properties due to coloring, a phosphorus antioxidant or a phenolic antioxidant is preferable, and a combination of a phosphorus antioxidant and a phenolic antioxidant is more preferable. When a phosphorus antioxidant and a phenolic antioxidant are used together, it is preferable to use the phosphorus antioxidant/phenolic antioxidant in a mass ratio of 0.2/1 to 2/1, and more preferably 0.5/1 to 1/1. desirable.

As the phosphorus antioxidant, 2,2-methylenebis(4,6-dit-butylphenyl)octylphosphite ("ADEKA STAB HP-10" manufactured by ADEKA Co., Ltd.), tris(2,4-dit-butyl Phenyl) phosphite (“IRGAFOS168” manufactured by BASF Japan Co., Ltd.), 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3, 9-diphosphaspiro[5.5]undecane ("ADEKA STAB PEP-36" manufactured by ADEKA Corporation, etc. is preferable.

As the phenolic antioxidant, pentaerythrityl-tetrakis[3-(3,5-dit-butyl-4-hydroxyphenyl)propionate] (“IRGANOX1010” manufactured by BASF Japan Co., Ltd., octadecyl-3 -(3,5-dit-butyl-4-hydroxyphenyl)propionate ("IRGANOX1076" by BASF Japan Co., Ltd.), etc. are preferable.

The thermal deterioration inhibitor can prevent thermal deterioration of the resin by replenishing polymer radicals generated when exposed to high temperatures under substantially oxygen-free conditions. As the thermal deterioration inhibitor, 2-t-butyl-6-(3'-t-butyl-5'-methyl-hydroxybenzyl)-4-methylphenyl acrylate ("Sumirizer GM" manufactured by Sumitomo Chemical Co., Ltd.), 2,4-di-t-amyl-6-(3',5'-di-t-amyl-2'-hydroxy-α-methylbenzyl)phenyl acrylate ("Sumirizer GS" manufactured by Sumitomo Chemical Co., Ltd.); desirable.

The ultraviolet absorber is a compound having an ability to absorb ultraviolet rays. The ultraviolet absorber is a compound that is said to have a function of mainly converting light energy into thermal energy. Examples of the ultraviolet absorber include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, oxalic acid anilides, malonic acid esters, and formamidines. Among these, benzotriazoles, triazines, or an ultraviolet absorber having a maximum value ε _max of the molar extinction coefficient at a wavelength of 380 to 450 nm of 1200 dm ³ ·mol ^-1 cm ^-1 or less are preferable. These ultraviolet absorbers may be used independently or may be used in combination of 2 or more types.

Benzotriazoles are highly effective in suppressing deterioration in optical properties such as coloration due to exposure to ultraviolet rays, and are therefore suitable as ultraviolet absorbers used when the resin composition of the present invention is applied to optical applications. As benzotriazoles, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol ("trade name TINUVIN329" manufactured by BASF Japan Co., Ltd.), 2-( 2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol ("trade name TINUVIN234" manufactured by BASF Japan Co., Ltd.), 2,2'-methylenebis[6-(2H -benzotriazol-2-yl)-4-tert-octylphenol] ("ADEKA STAB LA-31" by ADEKA Corporation), etc. are preferable.

Moreover, when intending to efficiently absorb the wavelength of wavelength 380 nm vicinity, triazine type ultraviolet absorber is used preferably. As such an ultraviolet absorber, 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine ("ADEKA STAB LA-F70" manufactured by ADEKA Co., Ltd.) ”), and hydroxyphenyltriazine-based ultraviolet absorbers (“TINUVIN477” and “TINUVIN460” manufactured by BASF Japan Co., Ltd.), which are analogs thereof, and the like.

The ultraviolet absorber containing sulfur in the skeleton can increase the refractive index of the resin composition in addition to the ultraviolet ray absorbing ability, so it is preferable when adapting the resin composition of the present invention to optical applications. Examples of ultraviolet absorbers containing sulfur in the skeleton include benzotriazoles, 2-(5-octylthio-2H-benzotriazol-2-yl)-6-tert-butyl-4-methylphenol (Compound A), 2-(5-dodecylthio-2H-benzotriazol-2-yl)-6-tert-butyl-4-methylphenol (Compound B). Also, as triazines, 2,4-diphenyl-6-(2-hydroxy-4-methylthiophenyl)-1,3,5-triazine (CompoundC), 2,4,6-(2-hydroxy) and oxy-4-hexylthiophenyl)-1,3,5-triazine (CompoundD).

The ultraviolet absorber containing sulfur in the skeleton can increase the refractive index of the resin composition, but may have absorption in the visible light region with a wavelength of 380 nm or more, which may cause the resin composition to be colored. Therefore, it is preferable to use together with another ultraviolet absorber.

When used in combination with ultraviolet absorbers, among the ultraviolet absorbers, benzotriazoles that do not contain sulfur in the skeleton [1], triazoles that do not contain sulfur in the skeleton [2], UV absorbers containing sulfur in the skeleton is written as [3], for example, [1] and [2]; [1] and [3] ; [2] and [3] : [1] and [2] and [3] ; A combination of In addition, [4] may be used in combination with a UV absorber that does not correspond to any of [1] to [3].

A light stabilizer is a compound that is said to have a function of trapping radicals mainly generated by oxidation by light. Preferred light stabilizers include hindered amines such as compounds having a 2,2,6,6-tetraalkylpiperidine skeleton. For example, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (made by ADEKA Corporation "Adecastab LA-77Y") etc. are mentioned.

A lubricant is a compound that is said to have an effect of improving releasability and workability by controlling the sliding between a polymer and a metal surface and preventing adhesion or sticking. Examples thereof include higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, fatty amides, and fatty acid esters. Among these, from the viewpoint of compatibility with the resin composition of the present invention, an aliphatic monohydric alcohol having 12 to 18 carbon atoms is preferable. For example, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, etc. are mentioned.

When the resin composition of the present invention contains other polymers and/or additives, they may be added during polymerization of the methacrylic resin (A) and/or the SMA resin (B), and the methacrylic resin (A) and the SMA resin (B) ) may be added when mixing, or may be added after mixing the methacrylic resin (A) and the SMA resin (B).

It is preferable that the range of the glass transition temperature of the resin composition of this invention is 115-160 degreeC. The lower limit of the glass transition temperature is more preferably 120°C or higher, still more preferably 130°C or higher, and most preferably 140°C or higher. Moreover, as for the upper limit of this glass transition temperature, it is more preferable that it is 155 degreeC or less, and it is still more preferable that it is 150 degreeC or less. When the glass transition temperature is in the range of 115 to 160°C, it is possible to suppress the occurrence of warping of the molded article made of the resin composition of the present invention at a high temperature.

The saturated water absorption of the resin composition of the present invention in water at 23°C is preferably 1.9% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1.0% by mass or less. When the saturated water absorption is 1.9% by mass or less, the resin composition of the present invention has excellent moisture resistance, and can suppress warpage of the laminate due to moisture absorption.

The MFR of the resin composition of the present invention is preferably in the range of 1 to 10 g/10 min. As for the lower limit of this MFR, it is more preferable that it is 1.5 g/10 min or more, and it is still more preferable that it is 2.0 g/10 min. Moreover, as for the upper limit of this MFR, it is more preferable that it is 7.0 g/10 min or less, and it is still more preferable that it is 4.0 g/10 min or less. When the MFR is in the range of 1 to 10 g/10 min, the stability of hot-melting molding is good.

The resin composition of this invention is extrusion molding methods, such as a coextrusion molding method, a T-die laminate molding method, and an extrusion coating method; injection molding methods such as an insert injection molding method, a two-color injection molding method, a core back injection molding method, a sandwich injection molding method, and an injection press molding method; blow molding method; calender molding method; press forming method; Various molded articles can be obtained by heat-melting molding by a method such as a slush molding method. Since the resin composition of the present invention hardly forms a gel even when melt-molded at high temperatures for a long time, it is also suitable for the production of molded articles that require high temperatures and long-term retention conditions. The resin composition of the present invention is suitable for producing thin and wide molded articles such as sheets, films, and plates.

[Laminate]

The laminate of the present invention has at least one layer made of the resin composition of the present invention (hereinafter also referred to as resin composition [C1]) and at least one layer made of another material. Other materials used in the laminate of the present invention are not particularly limited. For example, organic materials, such as resin; Inorganic materials, such as an elemental metal and a metal oxide, are mentioned.

A laminate according to an embodiment of the present invention has at least one layer made of the resin composition [C1] and at least one layer made of the resin composition [C2] as another layer.

The resin contained in the resin composition [C2] is not particularly limited. Examples of the resin include polyolefins such as polyethylene and polypropylene, polystyrene, (meth)acrylic resin, polyester, polyamide, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, and ethylene-vinyl Alcohol copolymer, polyacetal, polyvinylidene fluoride, polyurethane, modified polyphenylene ether, polyphenylene sulfide, silicone modified resin, polyether ether ketone, polysulfone, polyphenylene oxide, polyimide, polyetherimide, phenoxy resin; Thermosetting resins, such as a phenol resin, a melamine resin, a silicone resin, and an epoxy resin; An energy ray-curable resin etc. are mentioned. Resin of resin composition [C2] can be used individually by 1 type or in combination of 2 or more types. Among these, thermoplastic resins are preferred, and polycarbonates are more preferred.

When polycarbonate is used as the resin, the amount of polycarbonate contained in the resin composition [C2] is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 98% by mass or more. The weight average molecular weight of these polycarbonates is preferably from 20,000 to 100,000. When the weight average molecular weight of the polycarbonate is within the above range, the heat resistance and impact resistance of the resin composition [C2] are improved, and a laminated sheet composed of the resin composition [C1] and the resin composition [C2] can be obtained with excellent molding processability and high productivity. can be manufactured In addition, Mw/Mn of the polycarbonate is preferably 1.7 to 2.6, more preferably 1.7 to 2.3, still more preferably 1.7 to 2.0.

Commercially available products may be used for the above polycarbonate, for example, "Caliva (registered trademark)" by Sumika Styron Polycarbonate Co., Ltd., "Eupilon/Novalex (registered trademark)" by Mitsubishi Engineering Plastics Co., Ltd., Idemitsu Kosan "Taflon (registered trademark)" manufactured by Teijin Chemical Co., Ltd., "Panlight (registered trademark)" manufactured by Teijin Chemical Co., Ltd., and the like can be preferably used.

The resin composition [C2] used in the present invention is preferably a thermoplastic resin composition (T) having a glass transition temperature of 130 to 160°C. It is preferable that this thermoplastic resin composition (T) is a resin composition containing polycarbonate. Moreover, it is preferable that the glass transition temperature of resin composition [C2] is about the same as that of resin composition [C1]. Specifically, the absolute value |ΔTg| of the difference between the glass transition temperature of the resin composition [C2] and the glass transition temperature of the resin composition [C1] is preferably 30°C or less, more preferably 20°C or less. When |ΔTg| is 30°C or less, the effect of suppressing the occurrence of warping of the laminate under high temperature and high humidity is further enhanced.

It is preferable that the resin composition [C2] used for this invention is a thermoplastic resin composition (T) whose saturated water absorption in 23 degreeC water is 0.1-1.0 mass %. It is preferable that this thermoplastic resin composition (T) is a resin composition containing polycarbonate. Moreover, it is preferable that the saturated water absorption of resin composition [C2] is about the same as that of resin composition [C1]. Specifically, the absolute value of the difference between the saturated water absorption of the resin composition [C2] and the saturated water absorption of the resin composition [C1], Δsaturated water absorption|, is preferably 1.5% by mass or less, more preferably 1.0% by mass or less. When the difference in saturated water absorption between the two resins is 1.5% by mass or less, the effect of suppressing the occurrence of warping of the layered product under high temperature and high humidity is further enhanced.

The resin composition [C2] used in the present invention is preferably a thermoplastic resin composition (T) having a melt volume rate (hereinafter referred to as “MVR”) in the range of 1 to 30 cm 3 /10 min. The MVR is more preferably in the range of 3 to 20 cm 3 /10 min, and still more preferably in the range of 6 to 10 cm 3 /10 min.

In addition, the MVR in this specification is a value measured using a melt indexer under conditions of a temperature of 300°C and a load of 1.2 kg.

The resin composition [C2] used in the present invention may contain known additives in order to improve thermal decomposition resistance, thermal discoloration resistance, light resistance and the like. Examples of additives include antioxidants, thermal deterioration inhibitors, ultraviolet absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, salt pigments, light diffusing agents, organic dyes, gloss removers, impact resistance modifiers, and phosphors. can be heard

A laminate according to another embodiment of the present invention includes at least one layer [L1] made of the resin composition [C1], at least one layer [L2] made of the resin composition [C2], and at least one functional imparting layer [ L3]. The functional imparting layer [L3] is not particularly limited. Examples include a scratch-resistant layer, a hard coat layer, an antistatic layer, an antifouling layer, a friction reducing layer, an antiglare layer, an antireflection layer, an adhesive layer, and an impact strength imparting layer. The functional imparting layer [L3] can be formed by a known method. For example, a hard coat layer can be obtained by apply|coating the resin solution for hard coats, drying, and hardening. The antireflection layer can be obtained by laminating a low refractive index film and a high refractive index film by vapor deposition or the like. Of the functional imparting layer [L3], for example, a scratch resistance layer, a hard coat layer, an antistatic layer, an antifouling layer, a friction reducing layer, an antiglare layer, and an antireflection layer are generally formed on the outermost side of the laminate. As for the functional imparting layer [L3], only one type may be formed, or a plurality of types may be formed. The laminate of the present invention preferably has a scratch-resistant layer on at least one surface from the viewpoint of enhancing scratch resistance.

The layer structure in the laminate of the present invention is not particularly limited. In the lamination order of the laminate of the present invention, the layer made of the resin composition [C1] is the [L1] layer, the layer made of the resin composition [C2] is the [L2] layer, and the functional imparting layer [L3] is the [L3] layer. , for example, [L1] layer / [L2] layer, [L1] layer / [L2] layer / [L1] layer, [L2] layer / [L1] layer / [L2] layer, [L1] layer ] layer/[L2] layer/[L1] layer/[L2] layer/[L1] layer, [L1] layer/[L2] layer/[L3] layer, [L3] layer/[L1] layer/[L2] ] layer, [L3] layer/[L1] layer/[L2] layer/[L3] layer, [L3] layer/[L1] layer/[L2] layer/[L1] layer/[L3] layer, [L1 ] layer/[L2] layer/[L3] layer/[L2] layer/[L1] layer and the like. For example, when the [L3] layer is a hard coat layer, [L3] layer/[L1] layer/[L2] layer, [L3] layer/[L1] layer/[L2] layer/[L3] layer, [L3] layer/[L1] layer/[L2] layer/[L1] layer/[L3] layer are preferred.

INDUSTRIAL APPLICABILITY The present invention is useful for laminates in the form of sheets, thin plates, films and the like. When the laminate according to the present invention is used as a protective cover, it is preferable to arrange the resin composition [C1] layer outside the resin composition [C2] layer when viewed from the surface to be protected (the surface to be protected). For example, a laminate composed of a [L1] layer/[L2] layer may be arranged in the order of [L1] layer/[L2] layer/protected surface, or [L1] layer/[L2] layer. It is preferable to arrange a layered body composed of layers of /[L1] layers in the order of [L1] layer/[L2] layer/[L1] layer/protected surface.

The total thickness of the laminate according to the present invention can be set depending on the application, but is preferably 0.2 to 2 mm, more preferably 0.3 to 1.5 mm. If it is too thin, rigidity tends to be insufficient. When it is too thick, it tends to obstruct weight reduction of a liquid crystal display device or the like.

It is preferable that the range of the thickness of the layer which consists of resin composition [C1] in the laminate concerning this invention is 0.02-0.5 mm. As for the lower limit of the thickness of this layer, it is more preferable that it is 0.03 mm or more, and it is still more preferable that it is 0.05 mm or more. Moreover, as for the upper limit of the thickness of this layer, it is more preferable that it is 0.3 mm or less, and it is still more preferable that it is 0.1 mm or less. When this thickness is less than 0.01 mm, scratch resistance and weather resistance may be insufficient. Moreover, when it exceeds 0.5 mm, impact resistance may be insufficient.

From the viewpoint of suppressing the occurrence of warping under high temperature, the laminate according to the present invention is preferably made in a symmetrical stacking order in the thickness direction, and more preferably the thickness of each layer is also symmetrical.

The laminate according to the present invention is not particularly limited in terms of its manufacturing method, and can be produced, for example, by a multilayer molding method such as multilayer extrusion molding, multilayer blow molding, multilayer press molding, multicolor injection molding, or insert injection molding. there is. Among these multilayer molding methods, multilayer extrusion molding of the resin composition [C1] and the resin composition [C2] is preferred from the viewpoint of productivity.

The method of multilayer extrusion molding is not particularly limited, and a known multilayer extrusion molding method used for production of multilayer laminates of thermoplastic resins is employed. For example, an apparatus equipped with a flat T die and a polishing roll whose surface is mirror finished is molded by As the method of the T die, the feed block method in which the resin composition [C1] and the resin composition [C2] in a heated and molten state are laminated before entering the T die, or the resin composition [C1] and the resin composition [C2] are stacked inside the T die A stacked multi-manifold method or the like can be employed. A multi-manifold method is preferable from the viewpoint of enhancing the smoothness of the interface between the respective layers constituting the laminate.

Resin composition [C1] and resin composition [C2] are preferably melt-filtered with a filter before multilayer molding. Multilayer molding using each melt-filtered resin composition yields a laminated sheet with few defects derived from foreign matter, gel, or the like. The filter used for melt filtration is not particularly limited. The filter is appropriately selected from known ones from the viewpoints of operating temperature, viscosity, required filtration accuracy, and the like. As a specific example of a filter, Nonwoven fabric which consists of polypropylene, cotton, polyester, viscose rayon, glass fiber, etc.; phenolic resin impregnated cellulose film; metal fiber non-woven sintered film; metal powder sintering film; wire mesh; Or what is formed by combining these is mentioned. Among them, from the viewpoints of heat resistance, durability and pressure resistance, it is preferable to laminate and use a plurality of metal fiber nonwoven fabric sintered films.

The filtration accuracy of the filter is not particularly limited, but is preferably 30 μm or less, more preferably 10 μm or less, and still more preferably 5 μm or less.

According to the resin composition of the present invention, it has excellent transparency, surface hardness and heat resistance. Accordingly, molded articles and laminates obtained by melt-molding the resin composition according to the present invention have good appearance, excellent scratch resistance, and small dimensional change, and thus can be suitably used for optical members and the like.

As for the use of the molded article, molded article, and laminate concerning this invention, For example, signboard parts, such as an advertising tower, a stand signboard, a projecting signboard, a shop signboard, and a rooftop signboard; Display parts, such as a showcase, a partition board, and a shop display; Lighting parts, such as a fluorescent lamp cover, a mood lighting cover, a lamp shade, a light ceiling, a light wall, and a chandelier; interior parts such as pendants and mirrors; Building parts, such as a door, a dome, a safety window glass, a partition, a stair board, a balcony board, and the roof of a building for leisure; transport aircraft-related parts such as windshields for aircraft, visors for pilots, motorcycles, windshields for motor boats, visors for buses, side visors for automobiles, rear visors, headwings, and headlight covers; Electronic device parts, such as name plates for audio and video, stereo covers, television protection masks, and vending machine display covers; Medical device parts, such as an incubator and roentgen parts; Equipment-related parts, such as a machine cover, an instrument cover, an experiment device, a ruler, a dial, and an observation window; optical components such as liquid crystal protective plates, light guide plates, light guide films, Fresnel lenses, lenticular lenses, front plates of various displays, and diffusion plates; traffic-related parts such as road signs, information boards, curve mirrors, and sound barriers; film members such as surface materials for automobile interiors, surface materials for mobile phones, transparent conductive films, light guide films, polarizer protective films, and marking films; Members for home appliances, such as a cover material and control panel of a washing machine, and a cover panel of a warming rice cooker; Others include greenhouses, large-scale water tanks, box water tanks, clock panels, bath tubs, sanitaries, desk mats, organic parts, toys, masks for face protection during welding, and the like.

Examples and comparative examples are shown below to explain the present invention more specifically. However, the present invention is not limited to these examples.

[Resin composition] The physical properties of the resin compositions obtained in Examples 1a to 3a and Comparative Examples 1a to 6a were measured by the following method.

<Total light transmittance>

Using an injection molding machine (SE-180DU-HP manufactured by Sumitomo Heavy Machinery Co., Ltd.), the resin composition according to the present invention was injection molded under the conditions of a cylinder temperature of 280°C, a mold temperature of 75°C, and a molding cycle of 1 minute to obtain a thickness of 2 A square test piece of mm and a side of 50 mm was obtained. Based on the method of JIS-K7361-1, each test piece was measured using the Nippon Denshoku Industries Co., Ltd. spectroscopic color difference meter SE5000.

<Haze>

A test piece made of the resin composition according to the present invention was obtained by the same method as described above. Based on the method of JIS-K7361, each test piece was measured using the Nippon Denshoku Industries Co., Ltd. spectroscopic color difference meter SE5000.

<Rockwell Hardness>

A test piece made of the resin composition according to the present invention was obtained by the same method as described above. Based on the method of JIS-K7202-2, each test piece was measured by M scale using the Rockwell hardness tester DXT-FA by Toyo Seiki Co., Ltd.

<Glass transition temperature (Tg)>

In accordance with JIS K7121, the resin composition according to the present invention is heated from room temperature to 250 ° C at 20 ° C / min, held for 5 minutes, cooled to -100 ° C at 10 ° C / min, and then -100 ° C to 250 ° C Differential Scanning Calorimetry (DSC) analysis was performed under the temperature conditions in which the temperature was raised to °C at 10/min. The midpoint glass transition temperature obtained from the DSC curve measured at the time of the second temperature rise was employed as the glass transition temperature in the present invention. As a measuring device, Q-20 manufactured by TA INSTRUMENTS was used.

<Saturated water absorption>

A test piece made of the resin composition according to the present invention was obtained by the same method as described above. The test piece was vacuum-dried for 24 hours under conditions of a temperature of 80°C and 5 mmHg. Then, the test piece was left to cool in a desiccator. The test piece was taken out of the desiccator and the mass (initial mass) was measured immediately.

Then, the test piece was immersed in 23 degreeC distilled water. The test piece was taken out of the water, and the water adhering to the surface was wiped off to measure the mass. The test piece was immersed in distilled water, and the mass was measured in the same manner as above. Immersion in distilled water and mass measurement were repeated until there was no change in mass. The saturated water absorption was calculated from the mass (absorbed mass) when the mass change was eliminated and the initial mass by the following formula.

Saturated water absorption (%) = [(absorbed mass - initial mass) / initial mass] × 100

<Chemical resistance>

A test piece made of the resin composition according to the present invention was obtained by the same method as described above. 0.05 g of the sunscreen shown in Table 1 was uniformly applied to the surface of the test piece, and on top of it, two attached white cloths (single fiber cloth) for testing, an aluminum plate (75 mm × 150 mm × 1 mm), and a weight (500 g) were placed. and left at the temperature shown in Table 1 for 1 hour. Then, the weight, the aluminum plate, and the attached white cloth for the test were removed, and the surface of the test piece was washed with water with a nonwoven fabric wiper (Cotton Seagal) impregnated with a neutral detergent. After natural drying, the surface of the test piece was visually observed and evaluated according to the following criteria.

○: No change in appearance

△: There is no trace of white cloth attached, but whitening is slightly

×: There is a white cloth mark on the patch, and the whitening is markedly

<Examples of various materials>

For the methacrylic resin (A) and the vinyl copolymer (B) containing the resin composition according to the present invention, materials shown below were used.

Methacrylic resin (A1): Parapet manufactured by Kuraray Co., Ltd.

(Mw = 82,000, MMA copolymerization ratio = 100%, MA copolymerization ratio = 0%, rr ratio = 52%)

Methacrylic resin (A2): Parapet manufactured by Kuraray Co., Ltd.

(Mw = 120,000, MMA copolymerization ratio = 93.6%, MA copolymerization ratio = 6.4%, rr ratio = 48%)

Methacrylic resin (A3): Parapet manufactured by Kuraray Co., Ltd.

(Mw = 79,000, MMA copolymerization ratio = 88.7%, MA copolymerization ratio = 11.3%, rr ratio = 45%)

Vinyl copolymer (B): Regispy manufactured by Denki Chemical Industry Co., Ltd.

(Mw = 80,000, styrene/maleic anhydride/MMA = 56%/18%/26%)

<Example 1a>

70 parts by mass of a methacrylic resin (A1) and 30 parts by mass of a vinyl copolymer (B) were melt-kneaded with a twin screw kneader at a cylinder temperature of 230°C. Then, the molten resin was extruded to obtain a pellet-shaped resin composition [1]. Table 2 shows the composition of the resin composition [1] and the results of physical property evaluation.

<Example 2a>

A resin composition [2] was obtained in the same manner as in Example 1a, except that the composition ratio of the resin composition was 50 parts by mass of the methacrylic resin (A1) and 50 parts by mass of the vinyl copolymer (B). Table 2 shows the composition and physical properties of the resin composition [2].

<Example 3a>

A resin composition [3] was obtained in the same manner as in Example 1a except that the composition ratio of the resin composition was 30 parts by mass of the methacrylic resin (A1) and 70 parts by mass of the vinyl copolymer (B). Table 2 shows the composition and physical properties of the resin composition [3].

<Comparative Example 1a>

A resin composition [4] was obtained in the same manner as in Example 1a except for using the methacrylic resin (A2) instead of the methacrylic resin (A1). Table 2 shows the composition and physical properties of the resin composition [4].

<Comparative Example 2a>

A resin composition [5] was obtained in the same manner as in Example 2a except for using the methacrylic resin (A2) instead of the methacrylic resin (A1). Table 2 shows the composition and physical properties of the resin composition [5].

<Comparative Example 3a>

A resin composition [6] was obtained in the same manner as in Example 3a except for using the methacrylic resin (A2) instead of the methacrylic resin (A1). Table 2 shows the composition and physical properties of the resin composition [6].

<Comparative Example 4a>

A resin composition [7] was obtained in the same manner as in Example 1a except for using the methacrylic resin (A3) instead of the methacrylic resin (A1). Table 2 shows the composition and physical properties of the resin composition [7].

<Comparative Example 5a>

A resin composition [8] was obtained in the same manner as in Example 2a except for using the methacrylic resin (A3) instead of the methacrylic resin (A1). Table 2 shows the composition and physical properties of the resin composition [8].

<Comparative Example 6a>

A resin composition [9] was obtained in the same manner as in Example 3a except for using the methacrylic resin (A3) instead of the methacrylic resin (A1). Table 2 shows the composition and physical properties of the resin composition [9].

As the above results show, the resin compositions (Examples 1a to 3a) according to the present invention have high glass properties while maintaining transparency compared to the resin compositions (Comparative Examples 1a to 6a) according to the present invention having the same composition. Since it has a transition temperature, surface hardness and low saturated water absorption, it has excellent heat resistance, scratch resistance and moisture resistance. Moreover, it is excellent in chemical resistance.

[Laminate] The physical properties of the laminates obtained in Examples 1b to 3b and Comparative Examples 1b to 6b were measured by the following methods.

<transparency>

The total light transmittance of the laminate according to the present invention was measured in accordance with the method of JIS-K7361-1 using a spectral color difference meter SE5000 manufactured by Nippon Denshoku Industries Co., Ltd. In addition, the haze of the laminate according to the present invention was measured using the same apparatus as the total light transmittance in accordance with the method of JIS-K7361. Those having a total light transmittance of 90% or more and a haze of 0.3% or less were evaluated as ○, those having a total light transmittance of 90% or more or a haze of 0.3% or less were evaluated as △, and those having a total light transmittance of less than 90% and a haze of more than 0.3% were rated as ×.

<Pencil Hardness>

It was measured using a table-moving pencil scratch tester (Type P) (manufactured by Toyo Seiki Co., Ltd.). The presence or absence of scratches was confirmed while pressing the lead of a pencil at an angle of 45 degrees and a load of 750 g against the surface of the layer made of the resin composition of the laminate according to the present invention. The hardness of the lead of the pencil was increased in order, and the hardness of the lead that was one level softer than the time point at which scratches were generated was taken as the pencil hardness. The pencil hardness made ○ and the thing of F more than H into △, and made the thing less than F into x.

<Amount of warpage change>

A rectangular test piece with a short side of 65 mm and a long side of 110 mm was cut out from the laminate according to the present invention so that the direction perpendicular to the extrusion flow direction was the short side and the direction parallel to the extrusion flow direction was the long side. The short side of the test piece was hung and left to stand for 4 hours in an environmental tester set at a temperature of 75°C and a relative humidity of 50%, and then the test piece was left to cool at 25°C, and as a result, the test piece bent in a sliding manner. This is considered to be warpage caused by the influence of molding conditions. A test piece bent in a bow shape is placed on a surface plate so that the end of the test piece is in contact with the surface plate (that is, the test piece has a mountain shape), and the maximum distance between the surface plate and the test piece (usually, near the center of the long side of the test piece) is placed. becomes the maximum) was measured using a gap gauge. This value was made into the amount of initial warpage.

Then, the short side of the test piece bent in a bow was hung and left to stand for 72 hours in an environmental tester set at a temperature of 85°C and a relative humidity of 85%. After cooling the test piece for 4 hours in an environmental tester set at 25°C and 50% relative humidity, the maximum distance between the surface plate and the gap between the test piece was measured in the same manner as described above. The difference between this measured value and the initial amount of warpage was defined as the "change amount of warpage". The absolute value of the amount of warpage change was set to ○ for those less than 0.5 mm, △ for those of 0.5 or more and less than 1.0, and × for those of 1.0 mm or more.

<Chemical resistance>

The laminated body was cut out into a square of 50 mm on one side, and it was set as the test piece. 0.05 g of the sunscreen shown in Table 1 was uniformly applied to the surface of the layer made of the resin composition of the test piece, and two white cloths (single fiber cloth) for testing were applied thereon, an aluminum plate (75 mm × 150 mm × 1 mm), and A weight (500 g) was placed and left at the temperature shown in Table 1 for 1 hour. Then, the weight, the aluminum plate, and the attached white cloth for the test were removed, and the surface of the test piece was washed with water with a nonwoven fabric wiper (Cotton Seagal) impregnated with a neutral detergent. After natural drying, the surface of the test piece was visually observed and evaluated according to the following criteria.

○: No change in appearance

△: There is no trace of white cloth attached, but whitening is slightly

×: There is a white cloth mark on the patch, and the whitening is markedly

<Light resistance of polycarbonate layer>

A laminate test piece and a test piece of a single-layer film having a thickness of 80 μm of the resin compositions [1] to [3] without a polycarbonate layer were irradiated with ultraviolet rays, and the color difference (ΔE) was measured according to JIS Z-8730. The test piece of the laminate was irradiated with ultraviolet rays from the side of the resin composition [1] to [3] layers. The value obtained by subtracting the color difference of the resin composition single layer film from the color difference of the laminate having the polycarbonate layer was taken as the color difference of the polycarbonate layer.

Test Methods :

Tester: Ai Super UV Tester SUV-F1 type manufactured by Iwasaki Electric Co., Ltd.

Colorimeter: Color Analyzer C-2000 type manufactured by Hitachi, Ltd.

Exposure time: 24 hours

<Example 1b>

Pellets of polycarbonate (“SD Polycar (registered trademark) PCX” manufactured by Sumika Styron Polycarbonate Co., Ltd.) are set to a cylinder temperature of 245 to 260 ° C. and a discharge amount of 430 kg / hour. was added continuously. Pellets of the resin composition [1] were continuously introduced into a single screw extruder [II] having a diameter of 65 mm and set at a cylinder temperature of 215 to 230°C and a discharge amount of 37 kg/hour.

After simultaneously extruding the polycarbonate and the resin composition [1] from the extruder [I] and the extruder [II], and passing through a pleated cylindrical filter (manufactured by Fuji Filter Industry Co., Ltd.) having a filter hole size of 20 μm previously filled with resin, respectively, , Introduced into a junction block, and then, polycarbonate and resin composition [1] were co-extruded at a temperature of 245 ° C. with a multi-manifold die (Nordson Co., Ltd.) having a resin discharge port width of 1600 mm and a lip spacing of 2.0 mm to form a sheet. did This sheet was bank-molded between rolls 1 and 2 of the 4 horizontal rolls, and cooled while transferring the mirror surface with the 4 rolls to form a layer made of resin composition [1] with a thickness of 80 μm and polycarbonate with a thickness of 920 μm. A laminate having a total thickness of 1000 μm composed of layers comprising the above was obtained.

<Example 2b>

A layer made of the resin composition [2] having a thickness of 80 μm and a layer made of polycarbonate having a thickness of 920 μm were obtained in the same manner as in Example 1b except that the resin composition [1] was replaced with the resin composition [2], and the total thickness was 1000 μm. A laminate of was obtained.

<Example 3b>

A layer made of the resin composition [3] having a thickness of 80 μm and a layer made of polycarbonate having a thickness of 920 μm were obtained in the same manner as in Example 1b except that the resin composition [1] was replaced with the resin composition [3], and the total thickness was 1000 μm. A laminate of was obtained.

<Example 1c>

A laminate was obtained in the same manner as in Example 1b except that 1.0 parts by mass of a benzotriazole-based ultraviolet absorber (LA31RG; manufactured by Adeka) was added per 100 parts by mass of the resin composition [1]. ΔE of the polycarbonate layer by ultraviolet irradiation was 15 or more in Example 1b, but was 0.5 or less in Example 1c.

<Example 2c>

In Example 1c, except having changed to resin composition [2], it carried out similarly, and obtained the laminated body. ΔE of the polycarbonate layer was 0.5 or less in Example 2c, whereas it was 15 or more in Example 2b.

<Example 3c>

In Example 1c, except having changed to resin composition [3], it carried out similarly, and obtained the laminated body. ΔE of the polycarbonate layer was 0.5 or less in Example 3c, whereas it was 15 or more in Example 3b.

<Comparative Example 1b>

A layer made of the resin composition [4] having a thickness of 80 μm and a layer made of polycarbonate having a thickness of 920 μm in the same manner as in Example 1b except that the resin composition [1] was replaced with the resin composition [4], and a total thickness of 1000 μm A laminate of was obtained.

<Comparative Example 2b>

A layer made of the resin composition [5] having a thickness of 80 μm and a layer made of polycarbonate having a thickness of 920 μm in the same manner as in Example 1b, except that the resin composition [1] was replaced with the resin composition [5], with a total thickness of 1000 μm. A laminate of was obtained.

<Comparative Example 3b>

A layer made of the resin composition [6] having a thickness of 80 μm and a layer made of polycarbonate having a thickness of 920 μm in the same manner as in Example 1b, except that the resin composition [1] was replaced with the resin composition [6], with a total thickness of 1000 μm. A laminate of was obtained.

<Comparative Example 4b>

A layer made of the resin composition [7] having a thickness of 80 μm and a layer made of polycarbonate having a thickness of 920 μm in the same manner as in Example 1b, except that the resin composition [1] was replaced with the resin composition [7], with a total thickness of 1000 μm. A laminate of was obtained.

<Comparative Example 5b>

A layer made of the resin composition [8] having a thickness of 80 μm and a layer made of polycarbonate having a thickness of 920 μm were obtained in the same manner as in Example 1b except that the resin composition [1] was replaced with the resin composition [8], and the total thickness was 1000 μm. A laminate of was obtained.

<Comparative Example 6b>

A layer made of the resin composition [9] having a thickness of 80 μm and a layer made of polycarbonate having a thickness of 920 μm were obtained in the same manner as in Example 1b except that the resin composition [1] was replaced with the resin composition [9], and the total thickness was 1000 μm. A laminate of was obtained.

Table 3 shows the evaluation results of Examples 1b to 3b and Comparative Examples 1b to 6b.

As the above results show, the laminates (Examples 1b to 3b) according to the present invention have high pencil hardness and chemical resistance while maintaining transparency. In addition, it can be seen that the laminate according to the present invention has little warpage even when left to stand under high temperature and high humidity.

Claims (17)

5 to 90% by mass of a methacrylic resin (A) containing 100% by mass of a structural unit derived from methyl methacrylate, and at least a structural unit derived from an aromatic vinyl compound (b1) represented by the following general formula (1) and the following A resin composition containing 10 to 95% by mass of a vinyl copolymer (B) comprising a structural unit derived from a cyclic acid anhydride (b2) represented by the general formula (2) and having a glass transition temperature of 130°C or higher, wherein the methacrylic A resin composition characterized in that the resin (A) has a syndiotacticity (rr) of 50% or more in triplicate display.
[Formula 1]

(R ¹ and R ² in the formula each independently represent a hydrogen atom or an alkyl group)
[Formula 2]

(R ³ and R ⁴ in the formula each independently represent a hydrogen atom or an alkyl group) According to claim 1,
A resin composition containing 30 to 60% by mass of a methacrylic resin (A) and 40 to 70% by mass of a vinyl copolymer (B). According to claim 1,
The vinyl copolymer (B) contains 50 to 84% by mass of structural units derived from an aromatic vinyl compound (b1) and 15 to 49% by mass of structural units derived from a cyclic acid anhydride (b2), A resin composition containing 1 to 35% by mass of a structural unit derived from methacrylic acid ester (b3). According to claim 3,
A resin composition in which the methacrylic acid ester (b3) is methyl methacrylate. According to claim 1,
A resin composition having a glass transition temperature of 130 to 160°C. According to claim 1,
A resin composition containing an ultraviolet absorber. According to claim 6,
The resin composition characterized in that the ultraviolet absorber has a benzotriazole skeleton. According to claim 6,
The resin composition characterized in that the ultraviolet absorber has a triazine skeleton. According to claim 6,
The resin composition characterized in that the ultraviolet absorber contains sulfur in its skeleton. According to claim 6,
A resin composition containing two or more types of ultraviolet absorbers. A molded article provided with the resin composition according to any one of claims 1 to 10. A layer made of the resin composition according to any one of claims 1 to 10;
A laminate comprising a layer comprising a thermoplastic resin composition (T) having a glass transition temperature in the range of 130 to 160°C. According to claim 12,
A laminate in which the thermoplastic resin composition (T) is a resin composition containing polycarbonate. According to claim 12,
A laminate in which the absolute value of the difference between Tg of the thermoplastic resin composition (T) and the resin composition is 30°C or less. According to claim 12,
A laminate comprising a scratch-resistant layer on at least one surface. delete delete